CN108129602A - A kind of surface has microchannel hollow polymer elastic microsphere and its preparation method and application - Google Patents
A kind of surface has microchannel hollow polymer elastic microsphere and its preparation method and application Download PDFInfo
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- CN108129602A CN108129602A CN201611089124.7A CN201611089124A CN108129602A CN 108129602 A CN108129602 A CN 108129602A CN 201611089124 A CN201611089124 A CN 201611089124A CN 108129602 A CN108129602 A CN 108129602A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0462—Elimination of a polymeric phase using organic solvents
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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Abstract
The invention discloses a kind of surfaces to have microchannel hollow polymer elastic microsphere and its preparation method and application, the microballoon is hollow elasticity microballoon, shell is cross-linked polymer, surface has microchannel, the grain size of the elastic microsphere is 1~300 micron, the thickness of shell is 0.01~100 micron, and the aperture of microchannel is less than or equal to 0.05 micron.The microballoon has elastic restorability, and after filling some substances in the cavity of the hollow polymer elastic microsphere, in the case where no external force acts on, the substance in cavity can pass through the microchannel slow release of microballoon；When being acted on by external force, elastic deformation occurs for microballoon, the substance accelerated release in vitro in cavity；When removing external force, the microballoon deformed upon can restore to the original state again.The microballoon belongs to macromolecule polymer material, with performances such as low-density, good thermal insulation, sound insulation, light scattering, the fields such as medical treatment, cosmetics, cleaning/nursing materials (such as detergent, care agent), sewage disposal, catalyst loading are can be widely applied to.
Description
Technical field
The present invention relates to a kind of surface there is hollow polymer elastic microsphere of microchannel and its preparation method and application, belong to
In Functionally structure field.
Background technology
Polymeric hollow microsphere is that a kind of have polymeric shell layer and the internal microballoon for having cavity structure, this microballoon have low
The performances such as density, thermal insulation, sound insulation, good light scattering are widely used in catalyst loading, medicament slow release, cosmetics
The fields such as cladding, sewage disposal.
At present, preparing the main method of polymeric hollow microsphere has suspension polymerization, self-assembly method and solvent evaporation method, together
When, also soda acid swelling method, emulsion polymerization, template etc..It is to emulsify legal system using pik woods first for suspension polymerization
For w/o type droplet is gone out, these droplets are then dispersed in formation W/O/W type suspension systems in water phase, pass through heating
Initiator in oil phase causes polymerization, obtains the microballoon of water phase core, polymer shell, then by the methods of high temperature, etching by water phase
Core removes, and obtains polymeric hollow microsphere.It is in critical micelle concentration using amphiphilic block copolymer for self-assembly method
It can nearby be agglomerated into the principle of the closure globular micelle with interior outer double-layer structure in aqueous solution, introducing can gather in the copolymer
The function base of conjunction causes polymerization, you can obtain the polymeric hollow microsphere being combined with covalent bond.For solvent evaporation method, it is
First the polymer microballoon prepared is dispersed in water, then adds in a kind of good solvent in the system and goes to be swollen the microballoon, it is molten
After the completion of swollen, which is subjected to liquid nitrogen frozen so that the solvent swollen to inside microballoon is solidified as solid, then to the system
It is slowly heated up, the solvent inside microballoon is made slowly to vapor away, finally obtaining surface has the polymeric hollow microsphere of single hole.
In addition, Chinese patent CN102585279A, CN201410785640.8 and CN201510197352.5 are reported respectively
Using gaseous suspension method, oligomer pre-coating method and suspension polymerisation, closing method prepares surface and polymerize without permeability low-density in situ
The method of object microballoon.Gaseous suspension method (CN102585279A) has surface the porous or hollow micro- of water using the dry monomer of water speed is met
Ball surface hole carries out covering realization and it is closed, and is prepared for surface without osmotic polymer microballoon.Oligomer pre-coating method
(CN201410785640.8) there is, general poor compared with high viscosity and mobility using oligomer in organic good solvent
Oligomer is dissolved in volatile organic solvent, is made into the polymer solution of suitable viscosity, then adds in porous or hollow microsphere
Organic solvent is made to volatilize while stirring, obtain the polyalcohol stephanoporate or hollow microsphere of surface potential close.Suspension polymerisation is sealed in situ
Close method (CN201510197352.5) has the permeability microballoon of microchannel as seed using surface, has using monomer and polymer
There is the characteristics of good affinity, monomer is made to diffuse to seed microsphere surface and forms monomer liquid layer, then carries out home position polymerization reaction
Polymer coating closing microsphere surface duct is formed, obtains the surface of low-density closing without permeable hollow or porous microsphere.
To sum up, suspension polymerization, template, self-assembly method need molten by high temperature, calcining, organic solvent in preparation process
Swollen or etching processing, there is inconvenience in operating method, is not suitable for industrialized production.Surface is without permeable hollow or porous micro-
The preparation process of ball is prepared after being blocked to the duct of microsphere surface, because the duct before closure is larger, up to micron order, if
Without blocking its permeability clearly, but the step of closure increases the operation difficulty and homogeneity of preparation method.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of surfaces to have the hollow poly- of microchannel
Object elastic microsphere is closed, the elastic microsphere has special mechanical performance, organic solvent-resistant and temperature tolerance.
There is the preparation of the hollow polymer elastic microsphere of microchannel it is a further object to provide a kind of surface
Method can be prepared with special mechanical performance, organic solvent-resistant and durothermic surface using the method with microchannel
Hollow polymer elastic microsphere.
It is also another object of the present invention to provide the applications of above-mentioned hollow polymer elastic microsphere, are used for medical treatment, makeup
The fields such as product, cleaning/nursing materials (such as detergent, care agent), sewage disposal, catalyst loading.
To achieve these goals, the present invention provides following technical solutions：
A kind of surface has the hollow polymer elastic microsphere of microchannel, is hollow elasticity microballoon, and shell is poly- for crosslinking
Object is closed, the grain size of the elastic microsphere is 1~300 micron, and the thickness of the shell is 0.01~100 micron；Wherein, the bullet
Property microsphere surface there is microchannel, the aperture of the microchannel is less than or equal to 0.05 micron.
" elasticity " so-called in the present invention refers to：The microballoon have elasticity can recovery characteristics, i.e., it is micro- when being acted on by external force
Ball deforms upon, but after stress removal, and microballoon can restore the shape to deformation.The elasticity i.e. heretofore described bullet
The special mechanical performance of property microballoon.
According to the present invention, the grain size of the elastic microsphere is, for example, 100~250 microns, 100~200 microns, 30~150
Micron, 50~150 microns or 5~50 microns etc..
According to the present invention, the thickness of the shell is preferably 0.1~50 micron, for example, 5~30 microns, 1~15 micron,
3~20 microns, 10~20 microns or 0.5~6 micron etc..
According to the present invention, the aperture of the microchannel is also preferably less than micro- equal to 0.02 preferably smaller than equal to 0.03 micron
Rice.
According to the present invention, the microchannel on the elastic microsphere surface is perforation with internal cavity.
According to the present invention, the polymerized monomer of the cross-linked polymer includes monomer A and monomer B, and wherein monomer A is to make crosslinking
The monomer that polymer enbrittles, monomer B are to make the flexible monomer of cross-linked polymer.
Preferably, the monomer A includes one or more in styrene, methyl methacrylate, methyl acrylate；It is described
Monomer B includes methacrylic acid C3-5Arrcostab, acrylic acid C3-5It is one or more in Arrcostab.
It is further preferred that the monomer B includes methacrylic acid C4Arrcostab, acrylic acid C4Arrcostab, including C4
The various isomers of alkyl, such as n-BMA and n-butyl acrylate.
According to the present invention, the polymerized monomer of the cross-linked polymer can also further include monomer C, and wherein monomer C is
Adjust cross-linked polymer elasticity and/or brittle monomer.
Preferably, the monomer C includes one or two kinds of in ethyl methacrylate and ethyl acrylate.
According to the present invention, count by weight percentage, monomer A accounts for being more than or equal to for polymer quality to the cross-linked polymer
20wt% and less than 80wt%, monomer B accounts for polymer quality more than or equal to 20wt% and less than 80wt%.
Preferably, count by weight percentage, monomer A accounts for being more than or equal to for polymer quality to the cross-linked polymer
30wt% and less than 70wt%, monomer B accounts for polymer quality more than or equal to 30wt% and accounts for polymer less than 70wt%, monomer C
Quality is more than 0 and less than or equal to 60wt%.
Preferably, the crosslinking agent of the cross-linked polymer is divinylbenzene, cyclopentadiene, dicyclopentadiene or methyl ring
It is one or more in pentadiene.It is further preferred that the dosage of crosslinking agent is 20~50wt% of polymerized monomer quality.
The present invention also provides following technical solutions：
A kind of surface has the preparation method of the hollow polymer elastic microsphere of microchannel, includes the following steps：
1) oil-in-water type microlayer model suspension is prepared；
2) mixed solution containing polymerized monomer, initiator and crosslinking agent is prepared；Wherein, the polymerized monomer includes monomer
A and monomer B, wherein monomer A are the monomers that cross-linked polymer is made to enbrittle, and monomer B is to make cross-linked polymer flexible
Monomer；
3) at a certain temperature, the mixed solution of step 2) is added dropwise in the suspension of step 1), is reacted, described micro-
Droplet surface forms crosslinked polymeric shell layer；
4) regulate and control the temperature of reaction system and react again certain time at such a temperature, the hollow polymeric is prepared
Object elastic microsphere.
The method further includes following steps：
5) product of step 4) is further handled as follows：Flotation and drying.
According to the present invention, step 1) is specially：It first adds organic solvents into aqueous phase system, makes under stiring organic molten
Agent disperses in aqueous phase system, gradually heats up, and prepares oil-in-water type microlayer model suspension；Wherein, the aqueous phase system be dissolved with
The aqueous solution of colloid protective agent.
Wherein, the colloid protective agent is polyvinyl alcohol, for example, polyvinyl alcohol 1788.It is further preferred that the water phase body
In system, the mass percent of colloid protective agent is 0.5~5.0wt%.
Wherein, gradually heat up and cause system temperature (T1) stablize less than organic solvent boiling point (T0) 16~40 DEG C of temperature
Degree, i.e. T0(℃)-T1(DEG C)=16~40 (DEG C).Preferably, T0(℃)-T1(DEG C)=16~35 (DEG C)；It is further preferred that T0
(℃)-T1(DEG C)=16~30 (DEG C).
Wherein, the organic solvent is one kind in n-hexane, hexamethylene, normal heptane, isooctane, hexahydrotoluene.It is excellent
Selection of land, consumption of organic solvent are the 1~30wt%, further preferably preferably 5~25wt%, 5~20wt% of water quality.
According to the present invention, in step 2), the monomer A is included one in styrene, methyl methacrylate, methyl acrylate
Kind is a variety of；The monomer B includes methacrylic acid C3-5Arrcostab, acrylic acid C3-5It is one or more in Arrcostab.
Preferably, the monomer B includes methacrylic acid C4Arrcostab, acrylic acid C4Arrcostab, including C4Alkyl
Various isomers, such as n-BMA and n-butyl acrylate.
Preferably, the polymerized monomer can also further include monomer C, and wherein monomer C is to adjust cross-linked polymer bullet
Property and/or brittle monomer.
Preferably, the monomer C includes one or both of ethyl methacrylate and ethyl acrylate.
According to the present invention, in step 2), count by weight percentage, monomer A accounts for polymer quality to the cross-linked polymer
Be more than or equal to 20wt% and less than 80wt%, monomer B accounts for polymer quality more than or equal to 20wt% and less than 80wt%.
Preferably, count by weight percentage, monomer A accounts for being more than or equal to for polymer quality to the cross-linked polymer
30wt% and less than 70wt%, monomer B accounts for polymer quality more than or equal to 30wt% and accounts for polymer less than 70wt%, monomer C
Quality is more than 0 and less than or equal to 60wt%.
Wherein, the total dosage of the polymerized monomer is 60~150wt% of organic solvent quality.
Wherein, the crosslinking agent is one kind in divinylbenzene, cyclopentadiene, dicyclopentadiene, methyl cyclopentadiene
Or it is a variety of, dosage of crosslinking agent is 20~50wt% of polymerized monomer quality.
Wherein, the initiator is one kind in azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, is caused
1~3wt% of the agent dosage for polymerized monomer and crosslinking agent gross mass.
According to the present invention, in step 3), the reaction temperature (T2) control less than organic solvent boiling point (T0) 16~40 DEG C
Temperature, i.e. T0(℃)-T2(DEG C)=16~40 (DEG C), it is preferable that T0(℃)-T2(DEG C)=16~35 (DEG C), it is further preferred that T0
(℃)-T2(DEG C)=16~30 (DEG C)；0.5~4h of reaction time, preferably 0.5~2h.
According to the present invention, in step 4), regulate and control the temperature (T of reaction system3) to less than organic solvent boiling point (T0) 5~15
DEG C temperature, i.e. T0(℃)-T3(DEG C)=5~15 (DEG C), it is preferable that T0(℃)-T3(DEG C)=10~15 (DEG C).In the temperature
Under react 1~6h, preferably 2~4h again.
According to the present invention, in step 4), after reaction, system is cooled down and is down to room temperature, filtered, washing,
It air-dries and is dried in vacuo, obtain the hollow polymer elastic microsphere.
According to the present invention, the flotation of step 5) is impregnated and is settled for lower alcohol.
According to the present invention, step 5) is specially：The hollow polymer elastic microsphere of step 4) is dispersed in lower alcohol, no
Periodically stirring, some can be deposited to container bottom with the microballoon swum on lower alcohol liquid level, after its sedimentation completely, mistake
Filter takes the floating microballoon on top to obtain final hollow polymer elastic microsphere after air-drying and being dried in vacuo.
According to the present invention, in step 5), the sporadically stirring be specially every 1~2 hour with 300~400 turns/
The rotating speed stirring 5~20 minutes (such as 10 minutes) of min, operates continuously 10~15 times (such as 12 times), then stand 12 again~
36 hours (such as 24 hours).
According to the present invention, in step 5), the lower alcohol is C1-6Alkylol, preferably C1-4Alkylol, such as methanol, second
Alcohol, propyl alcohol or butanol etc., preferably ethyl alcohol.
The present invention further provides following technical solutions：
The application of above-mentioned hollow polymer elastic microsphere, the microballoon have it is preferable it is light scattering, thermal insulation harmony is exhausted
Edge also with characteristics such as special mechanical performance, organic solvent-resistant and temperature tolerances, can be widely applied to medical treatment, cosmetics, clear
The fields such as clean/nursing materials (such as detergent, care agent), sewage disposal, catalyst loading.
According to the present invention, the microballoon is used as reservoir, for example, can store drug, cleaning supplies, nursing materials,
Raw material, sewage-treating agent, catalyst of cosmetics etc..
Beneficial effects of the present invention：
It is good the present invention provides a kind of versatility and simple, efficiently prepare surface there is the hollow polymer bullet of microchannel
Property microballoon method, the microchannel on prepared hollow polymer elastic microsphere surface and internal cavity are perforations, can conduct
A kind of special reservoir, can be micro- by microchannel loading elasticity by some small-molecule substances under vacuum or negative pressure state
In the cavity of ball.The shell of the hollow polymer elastic microsphere reservoir has good elasticity, has both slow release and quick
The function of release.If in use, acted on without external force, the small-molecule substance in cavity can by the microchannel of elastic microsphere slowly to
Outer release；When being acted on by external force, elastic microsphere deforms upon, core small-molecule substance can by microchannel accelerated release in vitro, and
Stress is bigger, and release is faster；After stress removal, elastic microsphere has elastic recovery characteristics, can restore the shape to deformation,
The medium substance on inhalable periphery simultaneously, and the substance in original cavity and medium substance are diluted, then again may be used during stress simultaneously
Quick release.Also, by the regulation and control to polymerized monomer and dosage of crosslinking agent and ratio, can prepare different shell thicknesses and
The hollow polymer elastic microsphere of intensity further regulates and controls the relationship between external force and microballoon deformation.In addition, since shell is to hand over
The polymer of connection has insoluble insoluble property, both can also fill water-soluble substances with charge of oil soluble substance, also has good
Temperature tolerance.Hollow polymer elastic microsphere prepared by the method for the present invention also have it is preferable it is light scattering, thermal insulation harmony is exhausted
The characteristics such as edge can be widely applied to medical treatment, cosmetics, cleaning/nursing materials (such as detergent, care agent), sewage disposal, urge
The fields such as agent loading.
Specific embodiment
As previously mentioned, there is the preparation side of the hollow polymer elastic microsphere of microchannel the invention discloses a kind of surface
Method in the method, passes through the amount ratio to the amount ratio of water and organic solvent, organic solvent and polymerized monomer and crosslinking agent
Regulation and control make polymerisation mainly be carried out on oil-in-water type microlayer model surface, crosslinked poly- so as to be formed on the microlayer model surface
Close object shell；Secondly, by the regulation and control to temperature of reaction system, delay the organic solvent that part is wrapped in polymeric shell layer
Slow vaporization forms microchannel in microsphere surface, and the microchannel is perforation with internal cavity, and based on further place
Reason, filters out the better microballoon of connectivity wherein between the microchannel and internal cavities of microsphere surface；Further more, it selects suitably
Polymerized monomer and crosslinking agent, make the shell of hollow microsphere have elasticity.In addition, by polymerized monomer and dosage of crosslinking agent and ratio
Example regulation and control, different shell thicknesses and the hollow polymer elastic microsphere of intensity can be prepared, further regulate and control external force with it is micro-
Relationship between spherical shape change.
In the preferred embodiment of the present invention, the preparation method includes the following steps：First by organic solvent
It is added in the aqueous solution dissolved with protecting colloid, being stirred at room temperature makes the organic solvent dispersion gradually be risen into microlayer model state
The mixed solution of polymerized monomer, initiator and crosslinking agent is added dropwise in Wen Bingxiang systems.By the control to consumption of organic solvent, make
Polymerisation gradually carries out on the surface of organic solvent microlayer model, forms crosslinked polymeric shell layer.It is formed in polymeric shell layer
Initial stage by the regulation and control to system temperature, makes to be wrapped in the organic solvent in polymeric shell layer and slowly evaporates, and forms table
Face has the polymeric hollow microsphere of microchannel.Product is filtered, washing, air-dries, after vacuum drying, then it is carried out flotation-
Drying process process filters out the better microballoon of connectivity between the microchannel of microsphere surface and internal cavities.It is suitable to select
Polymerized monomer, can prepare shell have elasticity can recovery characteristics polymeric hollow microsphere, i.e., it is micro- when being acted on by external force
Ball deforms upon, and after stress removal, microballoon can restore the shape to deformation；Meanwhile by polymerized monomer and crosslinking agent
The regulation and control of dosage and ratio can prepare different shell thicknesses and the hollow polymer elastic microsphere of intensity.
In a preferred embodiment of the present invention, the preparation method specifically includes following steps：
(1) reactor equipped with blender and reflux condensate device is placed in water-bath, first adds in matter in backward reactor
The distilled water protecting colloid solution and quality that amount percentage is 0.5~5.0wt% are the organic molten of 5~20wt% of distillation water quality
Agent, adjusting mixing speed are 200~1500rpm, are stirred at room temperature 10 minutes, start to warm up and make system temperature (T1) stablize
Less than organic solvent boiling point (T0) 16~30 DEG C of temperature, i.e. T0(℃)-T1(DEG C)=16~30 (DEG C) form stable water
Oil-in microlayer model suspension.
(2) by polymerized monomer and quality that quality is 60~150wt% of organic solvent quality be polymerized monomer quality 20~
The crosslinking agent of 50wt% is placed in beaker, and adds in the initiator that quality is 1~3wt% of polymerized monomer and crosslinking agent gross mass,
Stirring is complete to initiator dissolving, forms uniform mixed solution.
(3) with the mixed solution of syringe pump a dropping step (2) into the suspension of step (1), after being added dropwise, keeping body
It is temperature (T2) less than organic solvent boiling point (T0) 16~30 DEG C of temperature, i.e. T0(℃)-T2(DEG C)=16~30 (DEG C), after
0.5~2h of continuous reaction.
(4) by system temperature (T3) rise to less than organic solvent boiling point (T0) 10~15 DEG C of temperature, i.e. T0(℃)-T3
(DEG C)=10~15 (DEG C), then react 2~4h.Then system is cooled down and is down to room temperature, filtered, water and ethyl alcohol difference
Washing 2 times, air-drying and surface is obtained after being dried in vacuo has the hollow polymer elastic microsphere of microchannel.
(5) the hollow polymer elastic microsphere that step 4) is prepared is dispersed in the beaker for filling ethyl alcohol, not timing
It is stirred (specifically, being stirred 10 minutes with the rotating speed of 300~400 turns/min every 2 hours, operate continuously 12 times,
Then 24 hours are stood again), some slowly can be deposited to beaker bottom with the microballoon swum on ethyl alcohol liquid level, treat that it is heavy
After drop is complete, filtering takes the floating microballoon on top to obtain surface micropore road and internal cavities perforation after air-drying and being dried in vacuo
The good hollow polymer elastic microsphere of property.
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after recorded content of the invention has been read, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
The performance test methods of elastic microsphere involved in the present invention are described below：
1. the macro-mechanical property test of elastic microsphere：
Take the glass slide S of a piece of 3.0cm*2.5cm*0.2cmUnder, the microballoon that stacking volume is 0.05~0.1mL is poured on this
Glass slide SUnderOn, microballoon is pushed open to individual layer with pan paper, individual layer microballoon occupied area is more than 1.0cm*1.0cm at this time；It chooses
As region to be measured, the microballoon in remaining region is gently removed with pan paper in accumulation most intensive most smooth 0.3cm*0.3cm regions；
By another 0.5cm*0.5cm*0.2cm glass slides SOnIt covers in microsphere surface to be measured, and by glass slide SUnder, glass slide SOnAnd microballoon
Entirety is moved on on the weight-scale table of electronic balance, in glass slide SOnMicroballoon region to be measured addition counterweight or other weights, Huo Zhezhi
It connects and presses glass slide S with forefingerOn, keeping force size, it is 30s to press the holding force time every time between 0.1N~30N, from
All around four direction respectively presses once；It presses and finishes, by glass slide SUnderAnd microballoon moves to rapidly optical microphotograph Microscopic observation,
Investigate microballoon rupture event and microballoon pressed after bounce situations.
2. microballoon organic solvent resistance is tested
0.1g microballoons is taken to add in tool plug sample bottle, 10g is then added in into sample bottle often with organic solvent, as ethyl alcohol,
Acetone, isopropanol, dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran, n,N-Dimethylformamide etc., naked eyes
Observe 1h, for 24 hours, the dissolving situation of microballoon in organic solvent after 168h, while microballoon is detached from solvent, in optical microphotograph
Whether Microscopic observation microballoon is swollen.If it is observed visually microballoon not dissolve in above-mentioned organic solvent, and optics is shown
Microballoon under micro mirror is not swollen, then it is assumed that microballoon organic solvent resistance is good.
The boiling point of organic solvent of the present invention at standard conditions is：
N-hexane：68.7℃；
Hexamethylene：80.7℃；
Normal heptane：98.5℃；
Isooctane：99.3℃；
Hexahydrotoluene：100.3℃.
With reference to specific embodiment, to preparing a kind of the specific of hollow polymer elastic microsphere of surface with microchannel
Operating procedure is described further.
Embodiment 1
A kind of surface has the preparation of crosslinked polystyrene-n-butyl acrylate hollow polymer elastic microsphere of microchannel
Method, concrete operation step are as follows：
(1) reactor equipped with blender and reflux condensate device is placed in water-bath, first adds in matter in backward reactor
It is different to measure polyvinyl alcohol 1788 (molecular weight 1700, alcoholysis degree 88%) aqueous solution 300.0g and 43.7g that percentage is 3wt%
Octane (99.3 DEG C of boiling point), adjusting mixing speed are 500rpm, are stirred at room temperature 10 minutes, start to warm up and make system temperature
Stablize at 71 DEG C, form stable oil-in-water type microlayer model suspension.
(2) 23.7g n-butyl acrylates, 23.0g styrene and 9.3g divinylbenzenes are placed in beaker, and add in
0.7g azodiisobutyronitriles stir to azodiisobutyronitrile dissolving completely, form uniform mixed solution.
(3) it at 71 DEG C, with the mixed solution of syringe pump a dropping step (2) into the suspension of step (1), is added dropwise
Afterwards, keeping the reaction temperature (71 DEG C), the reaction was continued 1.5 hours.
(4) system temperature is risen to 88 DEG C, then reacted 2.5 hours.Then system is cooled to room temperature, it is filtered,
Water and ethyl alcohol wash 2 times respectively, air-dry and crosslinked polystyrene-acrylic acid of the surface with microchannel is being obtained after being dried in vacuo just
Butyl ester hollow polymer elastic microsphere.
(5) the hollow polymer elastic microsphere that step 4) is prepared is dispersed in the beaker for filling ethyl alcohol, not timing
It is stirred (specifically, being stirred 10 minutes with the rotating speed of 300~400 turns/min every 2 hours, operate continuously 12 times,
Then 24 hours are stood again), some slowly can be deposited to beaker bottom with the microballoon swum on ethyl alcohol liquid level, treat that it is heavy
After drop is complete, filtering takes the floating microballoon on top to obtain surface micropore road and internal cavities perforation after air-drying and being dried in vacuo
Property good crosslinked polystyrene-n-butyl acrylate hollow polymer elastic microsphere.
The surface that embodiment 1 is prepared has crosslinked polystyrene-n-butyl acrylate hollow polymer of microchannel
Elastic microsphere has good hydrophobicity, and shell has certain elastic, non-friable.
The macro-mechanical property test of the microballoon shows：Applied force is in 30N or so, after all around respectively pressing four times,
Optical microphotograph Microscopic observation, more than 98% microballoon do not rupture, and about 60% microballoon is crushed；After standing 30 minutes, optics
Micro- Microscopic observation, the microballoon full recovery being crushed to original state.
Microspherulite diameter is cut between 50~250 μm, by microballoon with sharp instrument, observe its shell thickness 1~30 μm it
Between, the aperture of the microchannel is 0.05 μm.
Microballoon organic solvent resistance test shows：Microballoon has good organic solvent-resistant characteristic.
Embodiment 2
A kind of crosslinked polymethylmethacrylaparticles-n-butyl acrylate hollow polymer elasticity of surface with microchannel is micro-
The preparation method of ball, concrete operation step are as follows：
(1) reactor equipped with blender and reflux condensate device is placed in water-bath, first adds in matter in backward reactor
Measure percentage be 0.5wt% (molecular weight 1700, the alcoholysis degree 88%) aqueous solution of polyvinyl alcohol 1788 300.0g and 16g just
Hexane (68.7 DEG C of boiling point), adjusting mixing speed are 900rpm, are stirred at room temperature 10 minutes, start to warm up and make system temperature
Stablize at 49 DEG C, form stable oil-in-water type microlayer model suspension.
(2) 5.8g n-butyl acrylates, 11.6g methyl methacrylates and 4.0g dicyclopentadienes are placed in beaker,
And 0.3g azobisisoheptonitrile is added in, it stirs to azobisisoheptonitrile dissolving completely, forms uniform mixed solution.
(3) it at 49 DEG C, with the mixed solution of syringe pump a dropping step (2) into the suspension of step (1), is added dropwise
Afterwards, keeping the reaction temperature (49 DEG C), the reaction was continued 1 hour.
(4) system temperature is risen to 57 DEG C, then reacted 3 hours.Then system is cooled to room temperature, filtered, water
It is washed respectively with ethyl alcohol 2 times, air-drying and surface is obtained after being dried in vacuo has the crosslinked polymethylmethacrylaparticles-the third of microchannel
Olefin(e) acid N-butyl hollow polymer elastic microsphere.
(5) the hollow polymer elastic microsphere that step 4) is prepared is dispersed in the beaker for filling ethyl alcohol, not timing
It is stirred (specifically, being stirred 10 minutes with the rotating speed of 300~400 turns/min every 2 hours, operate continuously 12 times,
Then 24 hours are stood again), some slowly can be deposited to beaker bottom with the microballoon swum on ethyl alcohol liquid level, treat that it is heavy
After drop is complete, filtering takes the floating microballoon on top to obtain surface micropore road and internal cavities perforation after air-drying and being dried in vacuo
Property good crosslinked polymethylmethacrylaparticles-n-butyl acrylate hollow polymer elastic microsphere.
The surface that embodiment 2 is prepared has in crosslinked polymethylmethacrylaparticles-n-butyl acrylate of microchannel
Empty polymer elasticity microballoon has hydrophobicity, and shell thickness and hardness are moderate, non-friable.
The macro-mechanical property test of the microballoon shows：Applied force is in 30N or so, after all around respectively pressing four times,
Optical microphotograph Microscopic observation, more than 98% microballoon do not rupture, and about 70% microballoon is crushed；After standing 30 minutes, optics
Micro- Microscopic observation, the microballoon full recovery being crushed to original state.
Microspherulite diameter is cut between 30~200 μm, by microballoon with sharp instrument, observe its shell thickness 2~30 μm it
Between, the aperture of the microchannel is 0.02 μm.
Microballoon organic solvent resistance test shows：Microballoon has good organic solvent-resistant characteristic.
Embodiment 3
A kind of surface has crosslinked polystyrene-n-BMA hollow polymer elastic microsphere of microchannel
Preparation method, concrete operation step are as follows：
(1) reactor equipped with blender and reflux condensate device is placed in water-bath, first adds in matter in backward reactor
Measure polyvinyl alcohol 1788 (molecular weight 1700, alcoholysis degree 88%) aqueous solution 300.0g and 43.7g first that percentage is 5wt%
Butylcyclohexane (100.3 DEG C of boiling point), adjusting mixing speed are 1400rpm, are stirred at room temperature 10 minutes, start to warm up and make body
Be temperature stabilization at 75 DEG C, form stable oil-in-water type microlayer model suspension.
(2) 23.0g n-BMAs, 33.0g styrene and 12.0g divinylbenzenes are placed in beaker, and
0.9g azodiisobutyronitriles are added in, stirs to azodiisobutyronitrile dissolving completely, forms uniform mixed solution.
(3) it at 75 DEG C, with the mixed solution of syringe pump a dropping step (2) into the suspension of step (1), is added dropwise
Afterwards, keeping the reaction temperature (75 DEG C), the reaction was continued 1.5 hours.
(4) system temperature is risen to 90 DEG C, then reacted 3.5 hours.Then system is cooled to room temperature, it is filtered,
Water and ethyl alcohol wash 2 times respectively, and air-drying and surface is obtained after being dried in vacuo has crosslinked polystyrene-metering system of microchannel
Sour N-butyl hollow polymer elastic microsphere.
(5) the hollow polymer elastic microsphere that step 4) is prepared is dispersed in the beaker for filling ethyl alcohol, not timing
It is stirred (specifically, being stirred 10 minutes with the rotating speed of 300~400 turns/min every 2 hours, operate continuously 12 times,
Then 24 hours are stood again), some slowly can be deposited to beaker bottom with the microballoon swum on ethyl alcohol liquid level, treat that it is heavy
After drop is complete, filtering takes the floating microballoon on top to obtain surface micropore road and internal cavities perforation after air-drying and being dried in vacuo
Property good crosslinked polystyrene-n-BMA hollow polymer elastic microsphere.
The surface that embodiment 3 is prepared has crosslinked polystyrene-n-BMA of microchannel is hollow to gather
Closing object elastic microsphere has good hydrophobicity, and shell has certain elastic, non-friable.
The macro-mechanical property test of the microballoon shows：Applied force is in 30N or so, after all around respectively pressing four times,
Optical microphotograph Microscopic observation, more than 98% microballoon do not rupture, and about 40% microballoon is crushed；After standing 30 minutes, optics
Micro- Microscopic observation, the microballoon full recovery being crushed to original state.Microspherulite diameter is cut between 5~60 μm, by microballoon with sharp instrument
It opens, observes its shell thickness between 0.5~7 μm, the aperture of the microchannel is 0.02 μm.
Microballoon organic solvent resistance test shows：Microballoon has good organic solvent-resistant characteristic.
Embodiment 4
A kind of surface has crosslinked polystyrene-n-BMA-ethyl acrylate hollow polymeric of microchannel
The preparation method of object elastic microsphere, concrete operation step are as follows：
(1) reactor equipped with blender and reflux condensate device is placed in water-bath, first adds in matter in backward reactor
Measure polyvinyl alcohol 1788 (molecular weight 1700, alcoholysis degree 88%) aqueous solution 300.0g and 24.3g hexamethylene that percentage is 1%
Alkane (80.7 DEG C of boiling point), adjusting mixing speed are 1100rpm/min, are stirred at room temperature 10 minutes, start to warm up and make system
Temperature stabilization forms stable oil-in-water type microlayer model suspension at 60 DEG C.
(2) by 5.7g n-BMAs, 10.0g styrene, 1.0g ethyl acrylates and 5.0g dicyclopentadienes
It is placed in beaker, and adds in 0.4g azobisisoheptonitrile, stir to azobisisoheptonitrile dissolving completely, it is molten to form uniform mixing
Liquid.
(3) it at 60 DEG C, with the mixed solution of syringe pump a dropping step (2) into the suspension of step (1), is added dropwise
Afterwards, keeping the reaction temperature (60 DEG C), the reaction was continued 1 hour.
(4) system temperature is risen to 70 DEG C, then reacted 3 hours.Then system is cooled to room temperature, filtered, water
It is washed respectively with ethyl alcohol 2 times, air-drying and surface is obtained after being dried in vacuo has crosslinked polystyrene-methacrylic acid of microchannel
N-butyl-ethyl acrylate hollow polymer elastic microsphere.
(5) the hollow polymer elastic microsphere that step 4) is prepared is dispersed in the beaker for filling ethyl alcohol, not timing
It is stirred (specifically, being stirred 10 minutes with the rotating speed of 300~400 turns/min every 2 hours, operate continuously 12 times,
Then 24 hours are stood again), some slowly can be deposited to beaker bottom with the microballoon swum on ethyl alcohol liquid level, treat that it is heavy
After drop is complete, filtering takes the floating microballoon on top to obtain surface micropore road and internal cavities perforation after air-drying and being dried in vacuo
Property good crosslinked polystyrene-n-BMA-ethyl acrylate hollow polymer elastic microsphere.
The surface that embodiment 4 is prepared has crosslinked polystyrene-n-BMA-acrylic acid of microchannel
Ethyl ester hollow polymer elastic microsphere has hydrophobicity, and shell thickness and hardness are moderate, and with certain elasticity, non-friable.
The macro-mechanical property test of the microballoon shows：Applied force is in 30N or so, after all around respectively pressing four times,
Optical microphotograph Microscopic observation, more than 98% microballoon do not rupture, and about 60% microballoon is crushed；After standing 30 minutes, optics
Micro- Microscopic observation, the microballoon full recovery being crushed to original state.Microspherulite diameter is between 10~150 μm, by microballoon sharp instrument
It cuts, observes its shell thickness between 1~20 μm, the aperture of the microchannel is less than 0.02 μm.
Microballoon organic solvent resistance test shows：Microballoon has good organic solvent-resistant characteristic.
Embodiment 5-10
A kind of surface has crosslinked polystyrene-n-BMA-ethyl acrylate hollow polymeric of microchannel
The preparation method of object elastic microsphere
Other with embodiment 4, embodiment 5-10 only have polymerized monomer and crosslinking agent dosage and ratio and embodiment 4 not
Together, concrete numerical value is as listed in Table 1.
The numerical value of the macro-mechanical property of the product of embodiment 5-10 is given in table.
The macro-mechanical property of 1 embodiment 5-10 of table
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of surface has the hollow polymer elastic microsphere of microchannel, which is characterized in that the microballoon is micro- for hollow elasticity
Ball, shell are cross-linked polymer, and the grain size of the elastic microsphere is 1~300 micron, and the thickness of the shell is 0.01~100
Micron；Wherein, the elastic microsphere surface has microchannel, and the aperture of the microchannel is less than or equal to 0.05 micron.
Preferably, the grain size of the elastic microsphere be, for example, 100~250 microns, 100~200 microns, 30~150 microns, 50~
150 microns or 5~50 microns etc..
Preferably, the thickness of the shell be 0.1~50 micron, for example, 5~30 microns, 1~15 micron, 3~20 microns, 10
~20 microns or 0.5~6 micron etc..
Preferably, the aperture of the microchannel is less than or equal to 0.03 micron, also preferably less than equal to 0.02 micron.
2. hollow polymer elastic microsphere according to claim 1, which is characterized in that the micropore on the elastic microsphere surface
Road is perforation with internal cavity.
Preferably, the polymerized monomer of the cross-linked polymer includes monomer A and monomer B, and wherein monomer A is to have cross-linked polymer
There is brittle monomer, monomer B is to make the flexible monomer of cross-linked polymer.
Preferably, the monomer A includes one or more in styrene, methyl methacrylate, methyl acrylate；The monomer
B includes methacrylic acid C3-5Arrcostab, acrylic acid C3-5It is one or more in Arrcostab.
It is further preferred that the monomer B includes methacrylic acid C4Arrcostab, acrylic acid C4Arrcostab, including C4Alkyl
Various isomers, such as n-BMA and n-butyl acrylate.
Preferably, the polymerized monomer of the cross-linked polymer can also further include monomer C, and wherein monomer C is to adjust crosslinking
Polymer elasticity and/or brittle monomer.
Preferably, the monomer C includes one or two kinds of in ethyl methacrylate and ethyl acrylate.
Preferably, the cross-linked polymer count by weight percentage, the cross-linked polymer count by weight percentage, monomer
What A accounted for polymer quality is more than or equal to 20wt% and less than 80wt%, and monomer B accounts for polymer quality more than or equal to 20wt% and small
In 80wt%.
Preferably, the cross-linked polymer count by weight percentage, monomer A account for polymer quality be more than or equal to 30wt% and
Less than 70wt%, monomer B accounts for polymer quality more than or equal to 30wt% and accounts for the big of polymer quality less than 70wt%, monomer C
In 0 and less than or equal to 60wt%.
Preferably, the crosslinking agent of the cross-linked polymer is divinylbenzene, cyclopentadiene, dicyclopentadiene or methyl ring penta 2
It is one or more in alkene.It is further preferred that the dosage of crosslinking agent is 20~50wt% of polymerized monomer quality.
3. a kind of surface has the preparation method of the hollow polymer elastic microsphere of microchannel, which is characterized in that the preparation side
Method includes the following steps：
1) oil-in-water type microlayer model suspension is prepared；
2) mixed solution containing polymerized monomer, initiator and crosslinking agent is prepared；Wherein, the polymerized monomer include monomer A and
Monomer B, wherein monomer A are the monomers that cross-linked polymer is made to enbrittle, and monomer B is to make the flexible list of cross-linked polymer
Body；
3) at a certain temperature, the mixed solution of step 2) is added dropwise in the suspension of step 1), is reacted, in the microlayer model
Surface forms crosslinked polymeric shell layer；
4) regulate and control the temperature of reaction system and react again certain time at such a temperature, the hollow polymer bullet is prepared
Property microballoon.
4. preparation method according to claim 3, which is characterized in that the preparation method further comprises the steps：
5) product of step 4) is further handled as follows：Flotation and drying.
5. preparation method according to claim 3 or 4, which is characterized in that step 1) is specially：First organic solvent is added in
Into aqueous phase system, organic solvent is made to disperse in aqueous phase system under stiring, gradually heated up, prepared oil-in-water type microlayer model and hang
Supernatant liquid；Wherein, the aqueous phase system is the aqueous solution dissolved with colloid protective agent.
Preferably, the colloid protective agent is polyvinyl alcohol, for example, polyvinyl alcohol 1788.It is further preferred that the aqueous phase system
In, the mass percent of colloid protective agent is 0.5~5.0wt%.
Preferably, gradually heat up and cause system temperature (T1) stablize less than organic solvent boiling point (T0) 16~40 DEG C of temperature,
That is T0(℃)-T1(DEG C)=16~40 (DEG C).Preferably, T0(℃)-T1(DEG C)=16~35 (DEG C)；It is further preferred that T0(℃)-T1
(DEG C)=16~30 (DEG C).
Preferably, the organic solvent is one kind in n-hexane, hexamethylene, normal heptane, isooctane, hexahydrotoluene.
Preferably, consumption of organic solvent is the 1~30wt%, further preferably preferably 5~25wt%, 5~20wt% of water quality.
6. according to claim 3-5 any one of them preparation methods, which is characterized in that in step 2), the cross-linked polymer
Polymerized monomer include monomer A and monomer B, wherein monomer A is the monomer that cross-linked polymer is made to enbrittle, and monomer B is to make friendship
The flexible monomer of linked polymer.
Preferably, the monomer A includes one or more in styrene, methyl methacrylate, methyl acrylate；The monomer
B includes methacrylic acid C3-5Arrcostab, acrylic acid C3-5It is one or more in Arrcostab.
It is further preferred that the monomer B includes methacrylic acid C4Arrcostab, acrylic acid C4Arrcostab, including C4Alkyl
Various isomers, such as n-BMA and n-butyl acrylate.
Preferably, the polymerized monomer of the cross-linked polymer can also further include monomer C, and wherein monomer C is to adjust crosslinking
Polymer elasticity and/or brittle monomer.
Preferably, the monomer C includes one or both of ethyl methacrylate and ethyl acrylate.
Preferably, the cross-linked polymer count by weight percentage, monomer A account for polymer quality be more than or equal to 20wt% and
Less than 80wt%, monomer B accounts for polymer quality more than or equal to 20wt% and less than 80wt%.
Preferably, the cross-linked polymer count by weight percentage, monomer A account for polymer quality be more than or equal to 30wt% and
Less than 70wt%, monomer B accounts for polymer quality more than or equal to 30wt% and accounts for the big of polymer quality less than 70wt%, monomer C
In 0 and less than or equal to 60wt%.
Preferably, the total dosage of the polymerized monomer is 60~150wt% of organic solvent quality.
Preferably, the crosslinking agent for divinylbenzene, cyclopentadiene, dicyclopentadiene, one kind in methyl cyclopentadiene or
A variety of, dosage of crosslinking agent is 20~50wt% of polymerized monomer quality.
Preferably, the initiator be azodiisobutyronitrile, azobisisoheptonitrile, one kind in benzoyl peroxide, initiator
1~3wt% of the dosage for polymerized monomer and crosslinking agent gross mass.
7. according to claim 3-6 any one of them preparation methods, which is characterized in that in step 3), the reaction temperature (T2)
Control is less than organic solvent boiling point (T0) 16~40 DEG C of temperature, i.e. T0(℃)-T2(DEG C)=16~40 (DEG C), it is preferable that T0
(℃)-T2(DEG C)=16~35 (DEG C), it is further preferred that T0(℃)-T2(DEG C)=16~30 (DEG C)；0.5~4h of reaction time, it is excellent
Select 0.5~2h.
8. according to claim 3-7 any one of them preparation methods, which is characterized in that in step 4), regulate and control reaction system
Temperature (T3) to less than organic solvent boiling point (T0) 5~15 DEG C of temperature, i.e. T0(℃)-T3(DEG C)=5~15 (DEG C), it is preferable that
T0(℃)-T3(DEG C)=10~15 (DEG C).React 1~6h, preferably 2~4h again at such a temperature.
Preferably, in step 4), after reaction, system is cooled down and is down to room temperature, filtered, washing air-dries and true
Sky is dry, obtains the hollow polymer elastic microsphere.
9. according to claim 4-8 any one of them preparation methods, which is characterized in that the flotation of step 5) is impregnated for lower alcohol
And sedimentation.
Preferably, step 5) is specially：The hollow polymer elastic microsphere of step 4) is dispersed in lower alcohol, is sporadically stirred
It mixes, some can be deposited to container bottom with the microballoon swum on lower alcohol liquid level, and after its sedimentation completely, filtering takes
The floating microballoon in portion obtains final hollow polymer elastic microsphere after air-drying and being dried in vacuo.
Preferably, in step 5), the sporadically stirring is specially every 1~2 hour rotating speed with 300~400 turns/min
It stirs 5~20 minutes (such as 10 minutes), operates continuously 10~15 times (such as 12 times), then stand 12~36 hours (examples again
Such as 24 hours).
Preferably, in step 5), the lower alcohol is C1-6Alkylol, preferably C1-4Alkylol, as methanol, ethyl alcohol, propyl alcohol or
Butanol etc., preferably ethyl alcohol.
10. the surface described in claims 1 or 2 has the application of microchannel hollow polymer elastic microsphere, which is characterized in that institute
Stating microballoon has the preferable characteristics such as light scattering, thermal insulation and sound insulation, can be widely applied to medical treatment, cosmetics, cleaning/shield
Manage the fields such as articles for use (such as detergent, care agent), sewage disposal, catalyst loading.
Preferably, the microballoon is used as reservoir, such as can store drug, cleaning supplies, nursing materials, cosmetics
Raw material, sewage-treating agent, catalyst etc..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611089124.7A CN108129602B (en) | 2016-12-01 | 2016-12-01 | Hollow polymer elastic microsphere with micro-channels on surface and preparation method and application thereof |
Applications Claiming Priority (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103387625A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Preparation method and application of polystyrene hollow microspheres |
| CN103554325A (en) * | 2013-10-28 | 2014-02-05 | 北京化工大学 | Preparation method of functional hollow polymer microspheres |
| CN104086689A (en) * | 2014-07-03 | 2014-10-08 | 南京工业大学 | Large-particle-size high-crosslinking-degree hollow polymer microparticles and preparation method thereof |
| CN104844751A (en) * | 2015-05-17 | 2015-08-19 | 北京化工大学 | Micron-sized cross-linked polymer hollow microspheres and preparation method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387625A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Preparation method and application of polystyrene hollow microspheres |
| CN103554325A (en) * | 2013-10-28 | 2014-02-05 | 北京化工大学 | Preparation method of functional hollow polymer microspheres |
| CN104086689A (en) * | 2014-07-03 | 2014-10-08 | 南京工业大学 | Large-particle-size high-crosslinking-degree hollow polymer microparticles and preparation method thereof |
| CN104844751A (en) * | 2015-05-17 | 2015-08-19 | 北京化工大学 | Micron-sized cross-linked polymer hollow microspheres and preparation method for same |
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